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Living polymerization of azo monomers is one of the most effective ways to prepare well-de ned azo BCs. Generally, a monodispersed macroinitiator should be prepared rst. It is then used as an initiator for the subsequent polymerization of azo monomers. Finkelmann and Bohnert (1994) rst reported the synthesis of LC side chain AB azo BCs by direct anionic polymerization of an azo monomer. As shown in Scheme 12.1, the polymerization of polystyrene (PS)-based diblock copolymers was carried out from a PS-lithium capped with 1,1-diphenylethylene (DPE), whereas the poly(methyl methacrylate) (PMMA)-based diblock copolymers were prepared by addition of methyl methacrylate (MMA) monomers to the living azo polyanion, obtained by reaction of 1,1-diphenyl-3-methylpentylithium (DPPL) with the azo monomer in tetrahydrofuran (THF) at lower temperature. By this method, a series of well-de ned azo BCs were obtained with controlled molecular weights and narrow polydispersities (Lehmann et al., 2000). Although the living anionic polymerization technique is the most acceptable method for synthesis of well-de ned azo BCs because of the living nature of the end groups, this technique has some disadvantages too: 1. 2. 3. 4. Monomers and reagents should be highly pure. Very stringent drying is required. Puri cation of the living macroinitiator is dif cult. A low temperature is often needed (e.g., 701C).

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Method Photoelectric Photoelectric Photoelectric Contact potential versus Ta (110) Photoelectric Photoelectric Photoelectric Photoelectric Contact potential versus Ta (110) Contact potential versus Ta (110) Photoelectric Thermionic emission Thermionic emission Thermionic emission

Consider power and cooling features carefully when making decisions on chips used in your server blades.

Because of the aforementioned dif culties, many commercial polymers and copolymers (almost 50% of synthetic polymers) are prepared by radical processes. The major success of radical polymerization is the large number of monomers that can undergo free-radical polymerization, the convenient temperature range, and the

Cu (100) Cu(lll) Cu(110) Cu(112)

Scheme 12.1 Direct preparation of azo BCs by anionic living polymerization. Source: Reproduced with modi cations from Finkelmann and Bohnert, 1994.

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There are an infinite number of combinations here, only some of which will be considered (the individual steps are denoted by symbols as described on page 252): / 1 + / 2 ^ R ^Lt C(a) E(a) (EC) (b) C(b) (EC) (c) (5.6.1) p (CE) (a)

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In addition to the advances at the chip level, blade system vendors have also made great strides in power and cooling. One of the major sources of heat within servers has been due to inefficiencies of power supplies. For example, according to IBM, their 1U rack server power supply operated at 65% efficiency. This means that only 65% of the power that comes from the wall is converted into usable power by the server. The remaining 35% goes into the room in the form of heat. So for every 1 kW from the power provider, 650 W go to the server, and 350 W go into the room as heat. IBM s second generation of blade systems improved their power supplies to run at 91% efficiency, which translates to losing only 90 W as heat into the room. Similar advances in efficiency have come from others, such as HP, helping to make heat within the chassis less of an issue with newer blade server systems. Another area of improvement within the chassis comes from improved airflow within the chassis. One of the primary ways to improve cooling is to eliminate

R <=^ M = P E(b) R ^ P i + P2 C(c)

minimal requirement for puri cation of monomers and solvents, which should only be deoxygenated. Atom transfer radical polymerization (ATRP) method is one of the newly developed controlled/living radical polymerization, whose products always have well-de ned structures and low molecular-weight polydispersities (Matyjaszewski and Xia, 2001; Coessensm et al., 2001). Since the ATRP method allows for a control over the chain topology, composition, and end functionality for a large range of radically polymerizable monomers (Matyjaszewski and Xia, 2001), many azo BCs with speci ed structures have been synthesized by this simple approach (e.g., Yu et al., 2005c; Tang et al., 2007; Cui et al., 2005; Forcen et al., 2007; Han et al., 2004; He et al., 2003; Scheme 12.2). Recently, Iyoda and coworkers developed a modi ed ATRP method to prepare novel amphiphilic LC diblock copolymers consisting of a exible poly(ethylene oxide) (PEO) as a hydrophilic segment and poly(methacrylate) containing an azo moiety in the side chain as a hydrophobic LC segment (Tian et al., 2002). The unique characteristic of the amphiphilic azo LCBC lms is the nanoscaled microphase separation of a PEO nanocylinder (10 20 nm) regular array with a periodicity of B20 nm in an azo matrix. Starting from commercially available PEO, Yu et al. (2005c) applied this approach to prepare several wellspeci ed azo triblock copolymers with excellent photocontrol performances, as shown in Scheme 12.3. Besides the ATRP method, other controlled radical polymerization techniques such as reversible addition/fragmentation chain transfer polymerization (RAFT) (Zhang et al., 2007) and nitroxide-mediated polymerization (NMP) (Yoshida and Ohta, 2005), have also been explored to synthesize azo BCs.

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